Chromo- and fluorogenic Organometallic Sensors

Compounds that change their absorption and/or emission properties in the presence of a target ion or molecule have been studied for many years as the basis for optical sensing. Within this group of compounds, a variety of organometallic complexes have been proposed for the detection of a wide range of analytes such as cations (including H+), anions, gases (e.g. O2, SO2, organic vapours), small organic molecules, and large biomolecules (e.g. proteins, DNA). This chapter focuses on work reported within the last few years in the area of organometallic sensors. Some of the most extensively studied systems incorporate metal moieties with intense long-lived metal-to-ligand charge transfer (MLCT) excited states as the reporter or indicator unit, such as fac-tricarbonyl Re(I) complexes, cyclometallated Ir(III) species, and diimine Ru(II) or Os(II) derivatives. Other commonly used organometallic sensors are based on Pt-alkynyls and ferrocene fragments. To these reporters, an appropriate recognition or analyte-binding unit is usually attached so that a detectable modification on the colour and/or the emission of the complex occurs upon binding of the analyte. Examples of recognition sites include macrocycles for the binding of cations, H-bonding units selective to specific anions, and DNA intercalating fragments. A different approach is used for the detection of some gases or vapours, where the sensor's response is associated with changes in the crystal packing of the complex on absorption of the gas, or to direct coordination of the analyte to the metal centre.

Adsorption of sulfur dioxide on chemically modified natural clinoptilolite. Acid modification

Natural Bulgarian clinoptilolite from the south-eastern Rhodopes mountain was modified through treatment with hydrochloric acid with various normality, both single and repeatedly, as well as through a charring of a preliminary obtained NH4-form. The parameters concerning the uptake of the ion-exchangeable cations (Ca2+, Na+ and K+), as well as the uptake of aluminium from the natural material were calculated on the basis of the chemical contents. The highest extent of cations removal was attained in the case of the treatment with NH4Cl solution, while the highest aluminium deficiency was established in the samples treated by hydrochloric acid solutions with increasing concentration. Sulfur dioxide adsorption on the obtained decationised and dealuminised samples was studied according to the frontal-dynamic method. The parameters of the breakthrough curves, namely breakthrough time, saturation time and some of the statistical moments of the curve distribution, were determined. The dynamic adsorption capacities were also specified. Comparing the momentum values it was established that as a result of the natural zeolite treatment with NH4Cl and with low concentrated acid, the diffusion resistance decreases because of the dominant exchange of the presenting exchangeable cations in the samples with the smaller size protons and because of enlargement of the pores opening. Intensified dealuminisation was observed when more concentrated acid solutions are used. The capacity is enhanced, probably due to an increase in the total pore volume.

Ionic Liquids Containing Boron Cluster Anions

The combination of different boron cluster anions and some of the cations typically found in the composition of ionic liquids has been possible by straightforward metathetic reactions, producing new low melting point salts; the imidazolium cations have been systematically studied, [C(n)mim](+) (when [C(n)mim](+) = 1-alkyl-3-methylimidazolium; n = 2, 4, 6, 8, 10, 12, 14, 16, or 18). Melting points increase in the anionic order [Co(C2B9H11)(2)](-) =-34 degrees C). The salts [C(n)mim](2)[X] ([X](2-) = [B10Cl10](2-) or [B12Cl12](2-), n = 16 or 18) show liquid crystal phases between the solid and liquid states. Tetraalkylphosphonium salts of [B10Cl10](2-) have also been prepared. Physical properties, such as thermal stability, density, or viscosity, have been measured for some selected samples. The presence of the perhalogenated dianion [B12Cl12](2-) in the composition of the imidazolium salts renders highly thermally stable compounds. For example, [C(2)mim](2)[B12Cl12] starts to decompose above 480 degrees C in a dynamic TGA analysis under a dinitrogen atmosphere. Crystal structures of [C(2)mim][Co(C2B9H11)(2)] and [C(2)mim](2)[B12Cl12] have been determined. H-1 NMR spectra of selected imidazolium-boron cluster anion salts have been recorded from solutions as a function of the concentration, showing trends related to the cation-anion interactions.

Modulated electrostatic modes in pair plasmas: Modulational stability profile and envelope excitations

A pair plasma consisting of two types of ions, possessing equal masses and opposite charges, is considered. The nonlinear propagation of modulated electrostatic wave packets is studied by employing a two-fluid plasma model. Considering propagation parallel to the external magnetic field, two distinct electrostatic modes are obtained, namely a quasiacoustic lower moddfe and a Langmuir-like, as optic-type upper one, in agreement with experimental observations and theoretical predictions. Considering small yet weakly nonlinear deviations from equilibrium, and adopting a multiple-scale technique, the basic set of model equations is reduced to a nonlinear Schrodinger equation for the slowly varying electric field perturbation amplitude. The analysis reveals that the lower (acoustic) mode is stable and may propagate in the form of a dark-type envelope soliton (a void) modulating a carrier wave packet, while the upper linear mode is intrinsically unstable, and may favor the formation of bright-type envelope soliton (pulse) modulated wave packets. These results are relevant to recent observations of electrostatic waves in pair-ion (fullerene) plasmas, and also with respect to electron-positron plasma emission in pulsar magnetospheres. (c) 2006 American Institute of Physics.

Electrostatic mode envelope excitations in e-p-i plasmas - application in warm pair ion plasmas with a small fraction of stationary ions

The nonlinear propagation of amplitude-modulated electrostatic wavepackets in an electron-positron-ion (e-p-i) plasma is considered, by employing a two-fluid plasma model. Considering propagation parallel to the external magnetic field, two distinct electrostatic modes are obtained, namely a quasi-thermal acoustic-like lower mode and a Langmuir-like optic-type upper one. These results equally apply in warm pair ion ( e. g. fullerene) plasmas contaminated by a small fraction of stationary ions ( or dust), in agreement with experimental observations and theoretical predictions in pair plasmas. Considering small yet weakly nonlinear deviations from equilibrium, and adopting a multiple-scales perturbation technique, the basic set of model equations is reduced to a nonlinear Schrodinger (NLS) equation for the slowly varying electric field perturbation amplitude. The analysis reveals that the lower ( acoustic) mode is mostly stable for large wavelengths, and may propagate in the form of a dark-type envelope soliton ( a void) modulating a carrier wavepacket, while the upper linear mode is intrinsically unstable, and thus favours the formation of bright-type envelope soliton ( pulse) modulated wavepackets. The stability ( instability) range for the acoustic ( Langmuir-like optic) mode shifts to larger wavenumbers as the positive-to-negative ion temperature ( density) ratio increases. These results may be of relevance in astrophysical contexts, where e-p-i plasmas are encountered, and may also serve as prediction of the behaviour of doped ( or dust-contaminated) fullerene plasmas, in the laboratory.

Oblique modulation of electrostatic modes and envelope excitations in pair-ion and electron-positron plasmas

The nonlinear amplitude modulation of electrostatic waves propagating in a collisionless two-component plasma consisting of negative and positive species of equal mass and absolute charge is investigated. Pair-ion (e.g., fullerene) and electron-positron (e-p) plasmas (neglecting recombination) are covered by this description. Amplitude perturbation oblique to the direction of propagation of the wave has been considered. Two distinct linear electrostatic modes exist, namely an acoustic lower mode and Langmuir-type optic-type upper one. The behavior of each of these modes is examined from the modulational stability point of view. The stability criteria are investigated, depending on the electrostatic carrier wave number, the angle theta between the modulation and propagation directions, and the positron-to-electron temperature ratio sigma. The analysis shows that modulated electrostatic wavepackets associated to the lower (acoustic) mode are unstable, for small values of carrier wave number k (i.e., for large wavelength lambda) and for finite (small) values of the angle theta (yet stable for higher theta), while those related to the upper (optic-like) mode are stable for large values of the angle theta only, in the same limit, yet nearly for all values of sigma. These results are of relevance in astrophysical contexts (e.g., in pulsar environments), where e-p plasmas are encountered, or in pair fullerene-ion plasmas, in laboratory. (c) 2006 American Institute of Physics.

Nonlinear perpendicular propagation of ordinary mode electromagnetic wave packets in pair plasmas and electron-positron-ion plasmas

The nonlinear amplitude modulation of electromagnetic waves propagating in pair plasmas, e.g., electron-positron or fullerene pair-ion plasmas, as well as three-component pair plasmas, e.g., electron-positron-ion plasmas or doped (dusty) fullerene pair-ion plasmas, assuming wave propagation in a direction perpendicular to the ambient magnetic field, obeying the ordinary (O-) mode dispersion characteristics. Adopting a multiple scales (reductive perturbation) technique, a nonlinear Schrodinger-type equation is shown to govern the modulated amplitude of the magnetic field (perturbation). The conditions for modulation instability are investigated, in terms of relevant parameters. It is shown that localized envelope modes (envelope solitons) occur, of the bright- (dark-) type envelope solitons, i.e., envelope pulses (holes, respectively), for frequencies below (above) an explicit threshold. Long wavelength waves with frequency near the effective pair plasma frequency are therefore unstable, and may evolve into bright solitons, while higher frequency (shorter wavelength) waves are stable, and may propagate as envelope holes.(c) 2007 American Institute of Physics.

Low-frequency electrostatic defect mode in doped pair-ion plasmas

The nonlinear amplitude modulation dynamics of electrostatic oscillations of massive charged defects in a three-component pair plasma is investigated; i.e. doped pair-ion plasmas (anticipating the injection of a massive charged component in the background; e.g. in fullerene experiments). Ton-acoustic oscillations in electron-positron-ion (e-p-i) plasmas are also covered, in the appropriate limit. Linear and nonlinear effects (MI, envelope modes) are discussed. The role of the temperature and density ratio between the pair species is stressed.

Nonlinear Dynamics of Rotating Multi-Component Pair Plasmas and e-p-i Plasmas

The propagation of small amplitude stationary profile nonlinear electrostatic excitations in a pair plasma is investigated, mainly drawing inspiration from experiments on fullerene pair-ion plasmas. Two distinct pair ion species are considered of opposite polarity and same mass, in addition to a massive charged background species, which is assumed to be stationary, given the frequency scale of interest. In the pair-ion context, the third species is thought of as a background defect (e.g. charged dust) component. On the other hand, the model also applies formally to electron-positron-ion (e-p-i) plasmas, if one neglects electron-positron annihilation. A two-fluid plasma model is employed, incorporating both Lorentz and Coriolis forces, thus taking into account the interplay between the gyroscopic (Larmor) frequency ?c and the (intrinsic) plasma rotation frequency O0. By employing a multi-dimensional reductive perturbation technique, a Zakharov-Kuznetsov (ZK) type equation is derived for the evolution of the electric potential perturbation. Assuming an arbitrary direction of propagation, with respect to the magnetic field, we derive the exact form of nonlinear solutions, and study their characteristics. A parametric analysis is carried out, as regards the effect of the dusty plasma composition (background number density), species temperature(s) and the relative strength of rotation to Larmor frequencies. It is shown that the Larmor and mechanical rotation affect the pulse dynamics via a parallel-to-transverse mode coupling diffusion term, which in fact diverges at ?c ? ±2O0. Pulses collapse at this limit, as nonlinearity fails to balance dispersion. The analysis is complemented by investigating critical plasma compositions, in fact near-symmetric (T- ˜ T+) “pure” (n- ˜ n+) pair plasmas, i.e. when the concentration of the 3rd background species is negligible, case in which the (quadratic) nonlinearity vanishes, so one needs to resort to higher order nonlinear theory. A modified ZK equation is derived and analyzed. Our results are of relevance in pair-ion (fullerene) experiments and also potentially in astrophysical environments, e.g. in pulsars.

New ionic liquids from azepane and 3-methylpiperidine exhibiting wide

New ionic liquids based on azepanium and 3- methylpiperidinium cations have been synthesised; they exhibit moderate viscosities and remarkably wide electrochemical windows, thereby showing promise, inter alia, as electrolytes and battery materials, and as synthetic media.

A Frequency Domain Algorithm for Wave Separation

We propose a frequency domain adaptive algorithm for
wave separation in wind instruments. Forward and backward travelling waves are obtained from the signals acquired by two microphones placed along the tube, while the
separation ?lter is adapted from the information given by a
third microphone. Working in the frequency domain has a
series of advantages, among which are the ease of design of
the propagation ?lter and its differentiation with respect to
its parameters.
Although the adaptive algorithm was developed as a ?rst
step for the estimation of playing parameters in wind instruments it can also be used, without any modi?cations, for
other applications such as in-air direction of arrival (DOA)
estimation. Preliminary results on these applications will
also be presented.

Fabrication of cerium oxide nanoparticles: Characterization and optical properties

Ceria (CeO2) is a technologically important rare earth material because of its unique properties and various engineering and biological applications. A facile and rapid method has been developed to prepare ceria nanoparticles using microwave with the average size 7 nm in the presence of a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the nanoparticles were determined in depth with X-ray powder diffraction, transmission electron microscope, N-2 adsorption-desorption technique, dynamic light scattering (DLS) analysis, FTIR spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and Diffuse reflectance spectroscopy. The energy band gap measurements of nanoparticles of ceria have been carried out by UV-visible absorption spectroscopy and diffuse reflectance spectroscopy. The surface charge properties of colloidal ceria dispersions in ethylene glycol have been also studied. To the best of our knowledge, this is the first report on using this type of ionic liquids in ceria nanoparticle synthesis. (C) 2011 Elsevier Inc. All rights reserved.

Anion-templated formation of a unique inorganic 'super-adamantoid' cage [Ag-6(triphos)(4)(O3SCF3)(4)](2+) [triphos = (PPh2CH2)(3)CMe]

In the presence of templating anions, 2:3 molar mixtures of triphos and silver(I) cations unexpectedly give novel hexanuclear cages, which result from an unusual 'endo-methyl' geometry of the triphos ligands.

Orotate complexes of rhodium(I) and iridium(I): effect of coligand, counter ion, and solvent of crystallisation on association via complementary hydrogen bonding

The new complexes [NEt3H][M(HL)(cod)] (M = Rh 1 or Ir 2; H3L = 2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid, erotic acid; cod = cycloocta-1,5-diene) have been prepared by the reaction between [M2Cl2(cod)(2)] and erotic acid in dichloromethane in the presence of Ag2O and NEt3. They crystallise as dichloromethane adducts 1 . CH2Cl2 and 2 . CH2Cl2 from dichloromethane-hexane solutions. These isomorphous structures contain doubly hydrogen-bonded dimers, with additional hydrogen bonding to NEt3H+ cations and bridging CH2Cl2 molecules to form tapes. The use of (NBu4OH)-O-n instead of NEt3 gave the related complex [NBu4n][Rh(HL)(cod)] 1' which has an innocent cation not capable of forming strong hydrogen bonds and in contrast to 1 exists as discrete doubly hydrogen-bonded dimers. Complex 1' cocrystallises with 2,6-diaminopyridine (dap) via complementary triple hydrogen bonds to give [NBu4n][Rh(HL)(cod)]. dap . CH2Cl2 3. Complex 3 exhibits an extended sheet structure of associated [2 + 2] units, with layers of NBu4n, cations separating the sheets. These structural data together with those reported previously for platinum orotate complexes suggest that the steric requirements of the other ligands co-ordinated to the metal are important in influencing their hydrogen-bonding abilities. The solvent of crystallisation, the hydrogen-bonding propensity of the coligand and the nature of the counter ion also determine the type of association in the solid state.

On the self-aggregation and fluorescence quenching aptitude of surfactant ionic liquids

The aggregation behavior in aqueous solution of a number of ionic liquids was investigated at ambient conditions by using three techniques: fluorescence, interfacial tension, and H-1 NMR spectroscopy. For the first time, the fluorescence quenching effect has been used for the determination of critical micelle concentrations. This study focuses on the following ionic liquids: [C(n)mpy]Cl (1-alkyl-3-methylpyridinium chlorides) with different linear alkyl chain lengths (n = 4, 10, 12, 14, 16, or 18), [C(12)mpip]Br (1-dodecyl-1-methylpiperidinium bromide), [C(12)mpy]Br (1-dodecyl-3-methylpyridinium bromide), and [C(12)mpyrr]Br (1-dodecyl-1-methylpyrrolidinium bromide). Both the influence of the alkyl side-chain length and the type of ring in the cation (head) on the CMC were investigated. A comparison of the self-aggregation behavior of ionic liquids based on 1-alkyl-3-methylpyridinium and 1-alkyl-3-methylpyridinium cations is provided. It was observed that 1-alkyl-3-methylpyridinium ionic liquids could be used as quenchers for some fluorescence probes (fluorophores). As a consequence, a simple and convenient method to probe early evidence of aggregate formation was established.